Certain formylalkyl quaternary salts

ABSTRACT

Reactive N-substituted, cyclammonium quaternary salts wherein the N-substituent includes substituted alkyl radicals whose terminal carbon atom can be additionally substituted with, for example, a formyl radical, an acetal or thioacetal grouping including cyclic oxyacetals and cyclic thioacetals, or a hydrazono radical which is itself optionally substituted, are useful as chemical intermediates, as photographic addenda such as antifoggants or as nucleating agents in silver halide reversal emulsions. The salts are prepared by reacting a hydro salt of a cyclammonium base with an aliphatic organic compound having an active double bond system between the first and second carbon atoms.

United States Patent 91 Lincoln et al.

[ Apr. 29, 1975 [75] Inventors: Lewis L. Lincoln; Donald W.

Heseltine, both of Rochester, NY.

[73] Assignee: Eastman Kodak Company,

Rochester, NY.

221 Filed: on. 20, 1972 1211 Appl. No.: 300,559

Related US. Application Data [62] Division of Ser. No. 819,946, April28, I969, Pat.

No. 3,759.9Ul.

[52] US. Cl 260/286 Q; 260/298; 260/302 R; 260/302 F; 260/302 H;260/304; 260/307 R; 260/307 D; 260/309; 260/309.2; 260/326.l2;

260/326.l6 [5 l] Int. Cl C07d 91/44 [58] Field of Search 260/326.16,309, 307 R,

260/302 R, 298, 286 Q, 309.2, 304, 302 F, 307 D, 326.]2, 302 H [56]References Cited UNlTED STATES PATENTS 2,068,824 l/l937 Schonhofer et al260/286 Q 3,759,901 9/1973 Lincoln et al 260/240 G PrimaryExaminer-Richard J. Gallagher Attorney, Agent, or Firm-M. R. Chipaloski[57] ABSTRACT Reactive N-substituted, cyclammonium quaternary saltswherein the N-substituent includes substituted alkyl radicals whoseterminal carbon atom can be additionally substituted with, for example,a formyl radical, an acetal or thioacetal grouping including cyclicoxyacetals and cyclic thioacetals, or a hydrazono radical which isitself optionally substituted, are useful as chemical intermediates, asphotographic addenda such as antifoggants or as nucleating agents insilver halide reversal emulsions. The salts are prepared by reacting ahydro salt of a cyclammonium base with an aliphatic organic compoundhaving an active double bond system between the first and second carbonatoms.

10 Claims, No Drawings CERTAIN FORMYLALKYL QUATERNARY SALTS This is adivision, of application Ser. No. 819,946 filed Apr. 28, 1969 now US.Pat. No. 3,759,90l issued Sept. 18, 1973.

The present invention relates to organic synthesis and more particularlyto a novel method of preparing reactive, N-substituted, cyclammoniumquaternary salts, and to the salts prepared thereby.

It is an object of this invention to provide new compounds that arereactive quaternary salts of heterocyclic nuclei.

It is another object of the invention to provide a novel process forpreparing reactive quaternary salts of heterocyclic nuclei.

These and other objects of the instant invention will becomeadditionally apparent from a reading of the following specification andappended claims.

The objects of this invention are accomplished, in one aspect, withheterocyclic quaternary salts comprising a heterocyclic nucleuscontaining a heterocyclic ring of from to 6 atoms including a quaternarynitrogen atom which has substituted thereon a radical having the formula(CH-,),,R wherein:

a. n represents a positive integer having a value of from 2 to about 6,and

b. R represents a member selected from:

l. a formyl radical, 2. a radical having the formula wherein T, and Twhen taken alone, each represents a member selected from an alkoxyradical and an alkylthio radical, and T, and T when taken together,represent the atoms necessary to complete a cyclic acetal selected fromcyclic oxyacetals and cyclic thioacetals containing from 5 to 6 atoms inthe heterocyclic acetal ring, and

3. a hydrazonomethyl radical.

The subject quaternary salts also include heterocyclic quaternary saltscomprising a heterocyclic nucleus containing a heterocyclic ring of 5 to6 atoms including a quaternary nitrogen atom and from 4 to 5 additionalatoms of which from 3 to 4 atoms are carbon atoms and wherein theremaining additional atom is selected from the group consisting ofcarbon, nitrogen, oxygen, sulfur and selenium atoms. The quaternarynitrogen atom is substituted as described hereinabove.

Advantageously included within the subject invention are quaternarysalts having the formula:

wherein:

a. Z represents the non-metallic atoms necessary to complete aheterocyclic nucleus containing a heterocyclic ring of 5 to 6 atomsincluding the quaternary nitrogen atom, with the additional atoms ofsaid heterocyclic ring being selected from carbon, nitrogen, oxygen,sulfur and selenium, b. j represents a positive integer of from 1 to 2,c. 11 represents a positive integer of from 2 to 6, d. X represents anacid anion, e. R represents a member selected from:

1. a formyl radical, 2. a radical having the formula wherein T, and Twhen taken alone, each represents a member selected from an alkoxyradical and an alkylthio radical, and T, and T when taken together,represent the atoms necessary to complete a cyclic acetal selected fromcyclic oxyacetals and cyclic thioacetals containing from 5 to 6 atoms inthe heterocyclic acetal ring, and

3. a hydrazonomethyl radical, and f. R, represents either a hydrogenatom, an alkyl radical, an alkylthio radical or an aryl radical such asphenyl and naphthyl.

Exemplary heterocyclic nuclei completed by those atoms represented by Zare such nuclei as, for example, an indole nucleus, an imidazolenucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus,or a quinoline nucleus including those of the imidazole series such asbenzimidazole compounds like 5- chlorobenzimidazole and also includingcompounds of the naphthimidazole series; those of the thiazole seriessuch as thiazole, 4-methylthiazole, 4-phenylthiazole, S-methylthiazole,S-phenylthiazole, 4,5- dimethylthiazole, 4,5-diphenylthiazole, 4-(2-thienyl)thiazole, etc.; those of the benzothiazole series likebenzothiazole, 4-chlorobenzothiazole, 5- chlorobenzothiazole,6-chlorobenzothiazole, 7- chlorobenzothiazole, 4 4-methylbenzothiazole,5- methylbenzothiazole, 6-methylbenzothiazole, 5- bromobenzothiazole,6-bromobenzothiazole, 4- phenylbenzothiazole, S-phenylbenzothiazole, 4-methoxybenzothiazole, S-methoxybenzothiazole, 6- methoxybenzothiazole,S-iodobenzothiazole, 6- iodobenzothiazole, 4-ethoxybenzothiazole, 5-ethoxybenzothiazole, tetrahydrobenzothiazole,

5,6-dimethoxybenzothiazole, S-hydroxybenzothiazole,6-hydroxybenzothiazole, etc.; those of the naphthothiazole series suchas a-naphthothiazole, 8-methoxy-anaphthothiazole,7-methoxy-a-naphthothiazole, naphtho[2,l-d]thiazole,naphtho[2,3-d]thiazole, etc.; those of thethionaphtheno-7',6',4,5-thiazole series like 4'-methoxythionaphtheno-7,6, 4,5-thiazole, etc.; those of the oxazoleseries such as 4-methyloxazole, 5- methyloxazole, 4-phenyloxazole,4,5-diphenyloxazole, 4-ethyloxazole, 4,5-dimethyloxazole,S-phenyloxazole, etc.; those of the benzoxazole series like benzoxazole,5-chlorobenzoxazole, S-methylbenzoxazole, 5- phenylbenzoxazole,6-methylbenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole,5- methoxybenzoxazole, 5-ethoxybenzoxazole, 5- chlorobenzoxazole,6-methoxybenzoxazole, 5- hydroxybenzoxazole, 6-hydroxybenzoxazole, etc.;those of the naphthoxazole series such as a-naphthoxazole; those of theselenazole series like 4- methylselenazole, 4-phenylselenazole, etc.;those of the benzoselenazole series like benzoselenazole, 5-

chlorobenzoselenazole, 5-methoxybenzoselenazole,5-hydroxybenzoselenazole, tetrahydrobenzoselenazole, etc.; those of thenaphthoselenazole series such as oz-naphthoselenazole; and those of thequinoline series such as quinoline, lepidine. etc.

The acid anions represented by X include a wide variety of such anionsincluding halide anions like bromide, chloride and iodide, as well asadditional anions, e.g., sulfates including sulfate, hydrosulfate, andlower alkylsulfates like methylsulfate and ethylsulfate, aromaticsulfonates such as p-toluene sulfonate and benzenesulfonate, acid anionsderived from carboxylic acids like acetate, trifluoroacetate, propionateand a wide variety of other anions including anions such as, forexample, perchlorate, cyanate, thiocyanate, sulfamate, benzoate, etc.

Of the radicals represented by R, included are formyl, radicals asdescribed herein having the formula T1 at wherein T, and T when takenalone, each represent either an alkoxy radical typically having from 1to about 6 carbon atoms in the alkoxy chain or an alkylthio radicalpreferably having from 1 to 6 carbom atoms in the alkyl chain thereofand, when taken together, represent the atoms necessary to complete acyclic acetal which is either a cyclic oxyacetal or cyclic thioacetalradical such as 1,3-dithiolan-2-yl, 1,3- dioxolan-2-yl,1,3-dithian-2-yl, l,3-dioxan-2-yl and the like radicals; andhydrazonomethyl radicals including such substituted hydrazonomethylradicals as a thiosemicarbazonomethyl radical, a phenylhydrazonomethylradical like phenylhydrazonomethyl, p-tolylhydrazonomethyl,p-sulfophenylhydrazonomethyl, p-nitrophenylhydrazonomethyl, 2,4-dinitrophenylhydrazonomethyl, a benzothiazol-Z- ylhydrazonomethylradical, an N-phenylcarbamoylhydrazonomethyl radical and the likehydrazonomethyl radicals.

As employed herein, the terms alkyl radical, alkoxy radical andalkylthio radical include aliphatic, branched and straight chain alkyl,alkoxy and alkylthio radicals typically having from 1 to 6 carbon atomsin the alkyl moiety such as alkyl radicals like methyl, ethyl, propyl,isopropyl, n-butyl, tert-butyl, amyl, hexyl, etc.; alkoxy radicals suchas methoxy, ethoxy, propoxy, n-butoxy, tert-butoxy, and the like alkoxyradicals, and alkythio radicals like methylthio, ethylthio,tertbutylthio, hexylthio, etc. Preferably, the subject alkyl, alkoxy andalkylthio radicals have from 1 to 4 carbon atoms in the alkyl moietythereof, and they can be substituted or unsubstituted radicals. As usedherein, the term aryl radical comprehends such radicals as substitutedor unsubstituted phenyl and naphthyl radicals.

Of the reactive cyclammonium quaternary salts described herein,especially advantageous salts include those having theformula:

--Zr t r (:CII-C1'I)k-1 -R3 wherein:

a. Z represents the non-metallic atoms necessary to complete aheterocyclic nucleus such as those described elsewhere herein ascompleted by 2 atoms,

b. k represents a positive integer of from 1 to 2,

c. g represents a positive integer of from I to 5,

d. X represents an acid anion such as those described hereinabove,

e. R represents either a formyl radical or a radical having the formulawherein T and T are as defined for T and T and f. R represents asubstituent as defined for R Reactive quaternary salts of this inventioninclude such compounds as:

3-( Z-formylethyl )-Z-methylbenzothiazolium bromide,

3-( 3 ,3-dimethoxypropyl )-2-ethylbenzimidazolium chloride,

3-(3,3-diethoxypropyl)-2-methylbenzothiazolium iodide,

l (2-formylethyl)lepidinium bromide,

l-[2-( l,3-dithian-2-yl)ethyll-Z-ethylquinolium dide.

3-(3,3-diethoxypropyl)-2-methylbenzothiazolium perchlorate,

5-chloro-3-(2-formylethyl)-2- methylbenzoselenazolium bromide,

3-[3,3-di(ethylthio)propyll-Z-methylbenzothiazolium iodide,

3-[3,3-di(ethylthio)propyl]-2-methylbenzothiazolium p-toluene sulfonate,

l-(2-formylethyl)lepidinium bromide,

3-(3-formylpropyl)-2-ethylbenzimidazonium hydrosulfate,

3-( 6,6-diethoxy-n-hexyl )-2-methylnaphtho[ 2, l

d]thiazolium bromide,

3-[3,3-di(methylthio)propyll-Z-methylbenzothiazolium iodide,

3-(2-formylethyl)-2-methylbenzoselenazolium bromide,

3-( 3,3-diethylthiopropyl)-2-ethylbenzoxazolium bromide,

3-(2-formylethyl)-5,6-dimethoxy-2-methylbenzothiazolium bromide. otheruseful quaternary salts of the subject invention include hydrazonoalkylsubstituted salts having the formula:

"Z2 1 1 (=OH-CH) 1=-R5 I'I'J 9 t JHz 2) m-l wherein:

a, Z; represents the non-metallic atoms necessary to complete aheterocyclic nucleus such as those described elsewhere herein ascompleted by Z atoms,

b. p represents a positive integer of from 1 to 2,

c; m represents a positive integer of from 1 to 5,

d. R represents a hydrazonomethyl radical,

e. R represents a substituent as defined for R and f. X represents anacid anion.

Exemplary hydrazonomethyl radicals useful herein are, for example, thosehaving the formula M-N- HN=CH wherein M represents an aryl radical suchas phenyl or naphthyl which can be substituted with such substituents ashydroxy, alkyl, amino radicals like alkylamino, arylamino, heterocyclicamino, alkoxy, aryloxy, such amido radicals as acyloxy amidoacylcarbonamido, alkylcarbonamido, het rocyclic carbonamido,arylsulfonamide, alkylsulfonamido and heterocyclic sulfonamido.

Especially advantageous hydrazonoalkyl substituted quaternary salts ofthis invention include such salts as those described hereinabove whereinm is 1, R represents a methyl radical and R, represents ahydrazonomethyl such as:

. a phenylhydrazonomethyl radical,

. a p-tolylhydrazonomethyl radical,

. a p-sulfophenylhydrazonomethyl radical,

. a thiosemicarbazonomethyl radical,

. a benzothiazol-2-ylhydrazonomethyl radical, ap-carboxyphenylhydrazonomethyl radical,

g. a p-toluenesulfonylhydrazonomethyl radical,

h. a p-chlorophenylhydrazonomethyl radical,

i. a p-nitrophenylhydrazonomethyl radical,

j. an N-phenylcarbamoylhydrazonomethyl radical,

k. a 2,4-di(methylsulfo)phenylhydrazonomethyl radical,

l. a 2,4-dinitrophenylhydrazono radical, or

m. a 3-quinolylhydrazonomethyl radical.

Exemplary hydrazonoalkyl substituted quaternary salts of the inventioninclude such compounds as, for example:

3-[3-(benzothiazol-2-ylhydrazono)propyll-Z-methylbenzothiazolium iodide,

3-l3-(p-carboxyphenylhydrazono)propyl]-2-methylbenzoxazolium chloride,

3-[ 3-( p-carboxyphenylhydrazono )propyl benzothiazolium bromide,

2-methyl-3-[3-(ptoluenesulfonylhydrazono)propyl]naphtho[2,1 d]thiazoliumiodide,

3-[3-(p-chlorophenylhydrazono)propyl]naphtho[2,l-d]thiazolium bromide,

3-[ 3-( p-carboxyphenylhydrazono )propyl ]-2-ethyl- F O- UNnaphtho[2,l-d]thiazolium bromide,2-methyl-3-[(3-p-nitrophenylhydrazono)propyl]- naphtho[2,l-d]thiazoliumiodide, 2-methyl-3-[3-(N- phenylcarbamoylhydrazono)propyl]naphtho[2, ld]thiazolium iodide, 3-[3-(2,4-

dimethylsulfonylphenylhydrazono)propyl]-2- methylnaphtho[ 2, l -d]thiazolium bromide, 3-[3-(p-carboxyphenylhydrazono)propyl]-2-phenylbenzoselenazolium-p-toluene sulfonate,3-[(3-phenylhydrazono)propyl]benzothiazolium carboxylate,3-[(3-p-carboxyphenylhydrazono)propyll-2-methylbenzothiazolium bromide,3-[(3-p-carboxyphenylhydrazono)propyl]-5-chloro- Z-methylbenzothiazoliumbromide, 3-[3-(phenylhydrazono)propyl]benzothiazolium benzene sulfonate,2-ethyl-[ 3-( 3-p-sulfophenylhydrazono )propyl ]benzothiazolium iodide,3-[3-(p-sulfophenylhydrazono)propyl]benzothiazolium iodide, 2-methyl-3-[3-thiosemicarbazono )propyl]benzothiazolium bromide,2-methyl-3-[3-(thiosemicarbazono)propyl]benzothiazolium hydrosulfate,2-methyl-3-[(3-phenylhydrazono)propyllbenzothiazolium iodide,2-methyl-3-[(3-phenylhydrazono)propyl]benzothiazolium thiocyanate,2-methyl-3-[3-(p-tolylhydrazono)propyllbenzothioazolium iodide,2-methyl-3-[3-(p-sulfophonylhydrazono)propyl]- benzothiazolium chloride,2-methyl-3-[(3-thiosemicarbazono)propyl]benzothiazolium perchlorate,2-methyl-3-[ 3-phenylhydrazono )propyl benzothiazolium benzenesulfonate, 2-methyl-3-[3-(p-tolylhydrazono)propyl]benzothiazoliumacetate,

,2-methyl-3-[ 3-( p-sulfophenylhydrazono )propyllbenzothiazoliumpropionate, 2-methyl-3-[3-(benzothiazol-Z-ylhydrazono)propyl]-benzothiazolium cyanate,

5 ,6-dichlorol -ethyl-2-methyl-3-[ 3-(psulfophenylhydrazono)propyl]benzimidazolium bromide,

5,6-dichloro-3-[3-(2- benzothiazolylhydrazono )propyl]- l -ethyl-2-methylbenzimidazolium bromide,

5,6-dichloro-2-methyl-3-[ 3-( 3-quinolylhydrazono)propyll-lethylbenzimidazolium bromide,

5-chloro-2-methyl-3-[ 3-( p-tolylhydrazono)propyl]- benzoselenazoliumbromide,

2-methyl-3-[ 3-(ptoluenesulfonylhydrazono)propyl]benzothiazoliumbromide,

2-methyl-3-[3-(p-tolylhydrazono)propyl]benzothiazolium bromide,

3-[ 3-( 2,4-dinitrophenylhydrazono )propyl ]benzothiazolium bromide,

5 ,6-dichlorol -ethyl-2-methyl-3-[ 3-)ptolylhydrazonolpropyl]benzimidazolium bromide,

5,6-dichloro-l-ethyl-2-methyl-3-[3-(pnitrophenylhydrazono )propyl]benzimidazolium bromide,

wherein:

a. Z represents the atoms necessary to complete a heterocyclic nucleussuch as those defined hereinabove.

b.j represents a positive integer of from I to 2,

c. d represents a positive integer having a value of from I to 5,

d. X represents an acid anion,

e. R.,- represents:

l. a group having the formula W -C-'l wherein T represents a memberselected from a hydrogen atom, a hydroxyl radical, and alkyl radicalhaving preferably from I to 4 carbon atoms, and an alkoxy radicalpreferably having from 1 to 4 carbon atoms.

2. a sulfo radical, 3. a cyano radical, 4. an alkylsulfonyl radicalwherein the alkyl moiety has from 1 to 4 carbon atoms. and 5. a radicalhaving the formula wherein T, and T are as previously defined. and R, isas described in R,, said process comprising reacting a compound havingthe formula:

Z li (=CH-C ll) =d-R7 X 11 wherein Z. j. X and R, are as previouslydefined, with a compound having the formula:

LII

wherein d and R are as previously defined.

The reaction medium is advantageously an inert organic solvent thatexhibits moderate polarity and dissolves both the acid anion and thequaternary salt reagents, but which is not a solvent for the reactionproduct. Exemplary of such a medium are such solvents as acetonitrileand dimethylacetamide. No reaction catalysts are generally required andthe reaction temperature is conventionally variable from about 20C toabout 30C, although wider reaction temperature can be employed so longas the reagents remain in solution and are not subjected to heating inexcess of their decomposition temperatures. For example, refluxconditions can be employed to promote the reaction. The reactionproducts precipitate from solution and can then be purified by suchconventional means as solvent washing or sequential crystallization fromsolvents such as, for example, acetone, ethers, alcohols such asmethanol, ethanol and propanol, mixtures of alcohol and water, etc.

The subject advantageous processes also include a process for thepreparation of quaternary salts having the formula:

1 "I, I I =oHoH k ,=b-a,

llh l llfih-i wherein:

a. Z, represents the atoms necessary to complete a heterocyclic nucleus.such as defined hereinabove as represented by Z atoms,

b. k represents a positive integer of from 1 to 2,

c. b represents a positive integer of from 1 to 5,

d. X represents an acid anion,

e. R represents a member selected from a formyl radical and a radicalhaving the formula wherein T,, and T, are as defined for T, and T and f.R,, is as previously defined,

said process comprising reacting a compound having the formula:

wherein Z,, k, X. and R are as previously defined. with a compoundhaving the formula:

wherein b and R are as'previously defined.

Particularly advantageous processes include those for preparing thesalts mentioned immediately hereinabove wherein R, represents a methylradical, X represents a halide anion and b has a value of 1.

Additional reactive quaternary salts prepared according to the processesof this invention are the N- hydrazonoalkyl substituted quaternary saltsof the type described in detail hereinabove. The processes for preparinghydrazonoalkyl substituted salts include the process for preparingquaternarysalts having the formula:

--Z2 $1 (=oH-omm-1=o-R5 X H2 H2 2)el wherein:

a. 2 represents the atoms necessary to complete a heterocyclic nucleussuch as defined hereinabove as represented by Z atoms,

b. m represents a positive integer of from I to 2.

c. c represents a positive integer of from 1 to 5,

d. X represents an acid anion,

e. R represents a hydrazonomethyl radical, and

f. R; is as previously defined.

said process comprising the steps of:

a. reacting a compound having the formula:

wherein 2:, m. R and X are as previously defined, with a compound havingthe formula:

wherein c is as previously defined and T represents an acyl radical suchas a formyl radical, an acetyl radical. and a propionyl radical toprepare an intermediate compound having the formula:

"Z2 N (=CPIGH)m-1=CR5 10 p-carboxyphenylhydrazine,

p-tolylsulfohydrazine,

p-chlorophenylhydrazine,

p-nitrophenylhydrazine,

N-phenylcarbamoylhydrazine, and

2,4-di( methylsulfo )phenylhydrazine.

, Particularly advantageous processes include those for preparinghydrazonoalkyl substituted salts such as those described hereinabovewherein R represents a methyl radical, X represents a halide anion andthe hydrazonoalkyl radical represented by R, is selected from:

a. a phenylhydrazonomethyl radical.

b. a p-tolylhydrazonomethyl radical.

c. a p-sulfophenylhydrazonomethyl radical,

d. a thiosemicarbazonomethyl radical.

e. a benzothiazol-2-ylhydrazonomethyl radical,

f. a p-carboxyphenylhydrazonomethyl radical,

g. a p-tolylsulfohydrazonomethyl radical,

h. a p-chlorophenylhydrazonomethyl radical,

i. a p-nitrophenylhydrazonomethyl radical,

j. an N-phenylcarbamoylhydrazonomethyl radical,

k. a 2,4-di(methylsulfo)phenylhydrazonomethyl radical,

l. a 2,4-dinitrophenylhydrazono radical, or

m. a 3-quinolylhydrazonomethyl radical.

The conveniently prepared, reactive quaternary salts of this inventionare useful as photographic addenda in silver halide photographicemulsions and especially in gelatino-silver halide emulsionsas, forexample, antifoggants, etc., and as chemical intermediates in, forexample, the production of photographic dyestuffs by condensationreactions. Exemplary of a typical dye condensation to prepare asymmetrical photographic sensitizing dye is the reaction of a subjectquaternary salt with an excess amount (molar) of a condensing reagentsuch as diethoxymethyl acetate, 1,3,3-trimethoxypropene and the like.Unsymmetrical photographic dyes can be prepared by reacting thequaternary salts of this invention with a dye intermediate such aspdimethylaminobenzaldehyde, 5-acetanilidomethylene- 3-ethylrhodanine,3-ethylmercaptobenzothiazolium ethylsulfate, etc. The dyes so preparedare useful in photographic elements either as spectral sensitizers for aphotosensitive species such as silver halide or serving alternativefunctions wherein organic dyestuffs are advantageously employed.

The subject hydrazonoalkyl substituted quaternary salts are additionallyadvantageous as nucleating agents or fogging agents in silver halidereversal or direct positive emulsions used in positive-workingphotographic elements designed for reversal processing to prepare directpositive photographic images without utilizing an intermediate developednegative image. Such direct positive emulsions form latent i'magespredominantly inside the silver halide grains.

The photographic emulsions generally used in reversal processes aregelatino-silver halide emulsions such as silver bromide, silverbromoiodide or silver chloroiodide emulsions. They need not containsensitizing dyes although certain such dyes may be added to reversalemulsions for the purpose of inducing aerial fog, as well as to widenspectral sensitization. Internal latent image emulsions are typicallyundigested or if digested, the digestion is carried out without the useof surface sensitizers. An emulsion of this type, known as Burton'sHeterocyclic Quaternary Salt Melting Reagent Reaction Product PointYield -chloro-2-methyl- 5-chloro-3-( Z-formylcthyl 237- 5771benzothiazolium 2-methylbenzothiazolium 240C hydrobromide bromideS-methoxy-Z-mc- 3-(Z-formylethylJ-S-mcthoxy- 197- 70% thylbenzothiazol-2-methylbcnzothiazolium 198C ium hydrobromide bromide 5.6-dimethoxy-2-5,6-dimethoxy-3-( Z-formyloil 207!methylbenzothiethyl)-2-methylbenzothiazolium hydroazolium bromidebromide Z-methylnaphtho 3-(2-formylethyl)-2-methyloil 107: [2,3-dlthiazolium naphthol 2.3-d lthiazolium hydrobromide bromide4-methylquinolium l-( Z-formylcthyl )-4-mcthyl- 165- 7271 hydroiodidcquinolium iodide 167C emulsion is described in Wall Photographic Emu.sions," 1927, pp. 52 and 53. Further types of suitable reversalemulsions are internal latent image emulsions described in Davey andKnott. U.S. Pat. No. 2,592,250 and Luckey et al.. U.S. Pat. No.2,996,382.

The following examples are included for a further understanding of theinvention.

EXAMPLE 1 Preparation of 3-(2-formylethyl)-2-methylbenzothiazoliumbromide: Z-methylbenzothiazolium hydrobromide (1 mol., 11.5 g.) andacrolein (1 mol. 150% excess, 13.5 g.) are mixed in dimethylacetamide(150 ml.) and the mixture is stirred overnight at about 22C. The paleyellow solid which forms is then collected on a filter funnel. washedwith an excess of acetone and dried. The yield of crude salt is 110 g.(77%), mp. 249-250C dec.

EXAMPLE 2 Preparation of 5-chloro-3-(2-formylethyl)-2-methylbenzoselenazolium bromide: 5-chloro-2- methylbenzoselenazoliumbromide (1 mol., 31.1 g.) and acrolein (1 mol. 100% excess, 11.2 g.) aremixed in dimethylacetamide 100 ml.) and the mixture stirred overnight ata temperature of 22C. The white solid that forms is collected on afilter funnel, washed with acetone and dried. Yield of crude salt is 33g. (90%) EXAMPLE 3 Preparation 3 of 5.6-diehloro-l-ethyl-3-(2-formylethyl)-2-methylbenzimidazolium bromide: 5,6-dichloro-l-ethyl-2-methylbenzimidazolium hydrobromide (1 mol.. 31 g.)and acrolein (1 mol. 100% excess, l 1.2 g.) are mixed in 800 ml.dimethylacetamide, and the mixture is heated with stirring until allsolids are dissolved. The heat is then removed and the solution isstirred at 22C with stirring overnight. At this point ether l l.) isadded and the product precipitates from solution as a white solid. Thewhite solid is collected on a buchner funnel, washed with ether anddried. The product is used without further purification. Yield istheoretical, m.p. 279 to 281C.

EXAMPLE 4 EXAMPLE 5 Preparation of3-(3,3-diethoxypropyl)-2-methylhenzothiazolium iodide: 3-(Z-formylethyl)-2-methylbenzothiazolium iodide (1 mol., 64 g.) issuspended in absolute ethyl alcohol 150 ml.) with 30-32% hydrobromicacid in acetic acid (2 ml.) added, and the mixture is stirred at about22C one hour. A small portion of the alcohol solution is removed andstirred with an excess 5 of ether. Ether is then decanted from thesticky residue;

more ether is added with stirring; ether is again decanted, and thesticky residue stirred with a small amount of acetone. The stickyresidue dissolves in the acetone and the solution is treated with etherportionwise until it becomes cloudy, which cloudiness is followed by theproduct crystallizing from solution as a yellow solid. The main solutionis then treated with the seed crystals and stirred at room temperaturefor one hour. The yellow crystals are then collected on a filter funnel,washed with ether and dried. The yield of pure product is 48 g. (81%),mp. ll5-l 16C with dec. at C. Using procedures similar to those ofExamples 1, 2 and 3, additional compounds of this invention can beprepared conveniently by reacting a heterocyclic hydro salt reagent withadditional aliphatic compounds containing activated double bond systems.

EXAMPLE 6 Utilizing procedures like those of Example 1. the followingpreparations can be conveniently accomplished:

a. 1 -ethyl-2-methyl-3-( 2-propionylethyl )benzimidazolium bromide isprepared by reacting lethyl-2-methylbenzimidazolium hydrobromide andethylvinylketone,

b. 3-'(2-cyanoethyl)-2-methylbenz0xazolium iodide is prepared byreacting 2-methylbenzoxazolium hydroiodide and acrylonitrile.

c. 2-propyl-3-(2-carboxyethyl)naphtho[2.3-

dlselenazolium chloride is prepared by reacting 2-propylnaphthol2.3-d[selenazolium hydrochloride and acrylic acid.

d. 3-[ 3.3-di(ethylthio )propyl1-2-methylbenzothiazolium hydrosulfate isprepared by reacting Z-methylbenzothiazolium hydrosulfate and vinyldi-(ethylthio )methane-[ 3.3-di( ethylthio )propl -ene],

e. 3-[2-( l .3-dithiolan-2-yl)ethyll-2-ethylbenzothiazolium iodide isprepared by reacting 2-ethylbenzothiazolium hydroiodide and1,3-dithiolan-2- ylethylenc.

Additional reactive quaternary salts can be prepared 'in a similarfashion.

As described hereinabove, the subject hydrazonoalkyl substitutedquaternary salts are advantageous as nucleating (fogging) agents insilver halide reversal emulsions. Conventionally, those salts arereducing agents due to the presence of reactive substituents such ashydrazine derivatives. Exemplary preparations are described as follows.

EXAMPLE 7 Preparation of 2-methyl-3-thiosemicarbazonopropylbenzothiazolium bromide: thiosemicarbazide 1 mol. I071 excess, l g.) isdissolved in a refluxing solution of equal parts ethyl alcohol and water(150 ml.), and 3-(2-formylethyl)-2-methylbenzothiazolium bromideprepared according to the procedure of Example 1 is added, and allsolids are dissolved. Concentrated sulfuric acid (4 drops) is thenadded, and the entire solution is stirred for one-half hour. Thesolution is then chilled with stirring by means of an ice bath and afterseveral minutes, the product separates from solution as an oil thatquickly becomes crystalline. The light tan crystals are collected on afilter funnel, washed with acetone and dried. The yield of crude productis 20 g. (56% m.p. l77-l78C.

EXAMPLE 8 Preparation of 2-methyl-3-(3-phenylhydrazonopropyl)benzothiazolium bromide: 3-(2-formylethyl)-2-methylbenzothiazolium bromide (1 mol., 14.3 g.), asdescribed in Example I, is partially dissolved in ethyl alcohol 100 ml.)with stirring. Phenylhydrazine (1 mol. 10% excess, l 1.9 g.) is addedfollowed by the addition of concentrated sulfuric acid (4 g.) aredissolved in water 100 ml.) with stirring. After stirring at about 22Cone minute the product crystallizes from solution. The mixture isstirred at about 22C for 15 minutes, and the crystalline salt iscollected on a filter funnel, washed well with an excess of water anddried. After one recrystallization from a mixture of methyl alcohol andwater in a 1:1 ratio, the yield of product is 11 g. (56%), m.p. 163l64C.

EXAMPLE 10 Preparation of2-methyl-3-(psulfophenylhydrazonopropyl)benzothiazolium bromide:3-(2-formylethyl)-2-methylbenzothiazolium bromide (1 mol., 14.3 g.), asprepared in Example 1, is dissolved in water (200 ml.) with stirring,then gravity filtered and treated with a suspension ofp-hydrazino-benzene-sulfonic acid (1 mol., 9.4 g.) in water (400 ml.)with stirring. After minutes of stirring at about 22C., a buff coloredsolid precipitates from solution. After the entire solution has stirredat the 22C temperature, the solid is collected on a filter funnel,washed with an excess of water and dried. The product is then stirredwith refluxing methyl alcohol (500 ml.) collected on a filter funnel anddried. The

yield of product is 20 g. (87%), m.p. 258-259C.

EXAMPLE l 1 Preparation of 2-methyl-3-( benzothiazol-2-ylhydrazonopropyl)benzothiazolium bromide: 3-(2-formylethyl)-2-methylbenzothiazolium bromide (1 mol., 14.3 g.), asprepared in Example 1, and 2- hydrazinobenzothiazole (1 ml., 8.15 g.)are mixed in ethyl alcohol (150 ml.) with stirring at about 22C.Concentrated sulfuric acid (4 drops) is added whilemethylbenzimidazolium hydrobromidc and 3- hydrazinoaquinolinc propylll-ethylbcnzimidazolium bromide drops), and the mixture is Stirred atabout 22 f 15 stirring is continued, and the entire mixture is stirredat minutes. At this point, heat is applied, the mixture is aboutThefnlxture heated to f heated to reflux temperature with stirring andthe prod- Perature f u fi g, and ltile plrodulctj precrlrirtateg uct iscrystallized from solution as a white solid. The from Sohmon as whlte :9e T z solid is collected on a filter funnel, washed with ethyl 40 from tg f 5 wasde l alcohol and dried. After one recrystallization fromwaexcess y c0 0 an 6 pm uc en the yield of product is 10 g (53%) m prefluxed in ethyl alcohol (200 ml.) collected on afilter o oc funnel anddried. Yield of white solid is 16 g. (90%),

' m.p. l60l6lC with dec.

EXAMPLE 9 EXAMPLE 12 Preparation of y -P- Utilizing procedures likethose described in Examtolylhydrazon propyl) z h li bromide: ples 741,additional hydrazonoalkyl substitutedquaformylethyl)-2methylbenZ0thiaZOlium bromide l ternary salts areprepared. The reagents, reaction prod- 143 g.). as pr p e in Ex mp andP- ucts,yield and melting points are summarized below in tolylhydrazinehydrochloride (1 mol. 10% excess, 8.7 b l f Reaction Melting ReagentsProduct Point Yield 5 ,o-dichlorol -cthyl- 5 ,6-dichloro l -ethyl-2-289- 4071 3-(2-formylethyl)-2- methyl-3-[3-(p-sulfo- 290Cmethylbenzimidazolium phenylhydrazono )propyl] dec. hydrobromide andpbenzimidazolium bromide sulfophenylhydrazine 5,6-dichlorol -cthyl-5.6-dichloro-3-l 3-( 2- 39% 3-( Z-formylcthyl )-2-bcnzothiazolylhydrazono) l4 1 C methylhcnzimidazolium propyl ll-ethyl-2-methyldec. hydrobromidc and 2- henzimidazolium bromidehenzothiazolylhydra- Zine 5,6-dichlorol -cthyl-5,b-dichloro-Z-mcthyl-fl- 191-- 3-( Z-formylethyl )-2- [343-quinolylhydrazono) l92C. 25%

The invention has been described in detail with particular reference topreferred embodiments thereof, but, it will be understood thatvariations and modifications can be effected within the spirit and scopeof the invention. I

We claim:

1. A quaternary salt having the formula:

wherein:

a. Z, represents the atoms necessary to complete a heterocyclic nucleusselected from the group consisting of an indole nucleus, an imidazolenucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleusand a quinoline nucleus,

b. k represents a positive integer of from 1 to 2,

c. g represents a positive integer of from 1 to 5,

d. X represents an acid anion,

e. R represents a formyl radical, and

f. R represents a member selected from the group consisting of ahydrogen atom, a C C,, alkyl radical, a C -C alkylthio radical phenyland naphthyl.

2. A quaternary salt having the formula:

CH X9 (=eH-CH) 3 wherein:

a. 2 represents the atoms necessary to complete a heterocyclic nucleusselected from the group consisting of an indole nucleus, an imidazolenucleus, an oxazole nucleus. a thiazole nucleus, a selenazole nucleusand a quinoline nucleus,

b. 1 represents a positive integer of from 1 to 2.

c. X represents a halide anion, and

d. R- represents a formyl radical.

3. 3-(2-Formylethyl)-2-methylbenzothiazolium bromide.

4. 5-Chloro-3-(2-formylethyl)-2- methylbenzoselenazolium bromide.

5. 5.6-Dichloro-l-ethyl-(2-formylethyl)-2- methylbenzimidazoliumbromide.

6. 5-Chloro-3-( 2-formylethyl )-2-methylbenzothiazolium bromide.

7. 3-(2-Formylethyl)-5-methoxy-2-methylbenzothiazolium bromide.

8. 5,6-Dimethoxy-3-(2-formylethyl)-2-methylbenzothiazolium bromide.

9. 3-(2-Formylethyl)-2-methylnaphtho[2,3-

dlthiazolium bromide.

10. 1-(2-Formylethyl)-4-methylquinolium iodide.

1. A QUATERNARY SALT HAVING THE FORMULA:
 2. A quaternary salt having theformula:
 3. 3-(2-Formylethyl)-2-methylbenzothiazolium bromide. 4.5-Chloro-3-(2-formylethyl)-2-methylbenzoselenazolium bromide. 5.5,6-Dichloro-1-ethyl-(2-formylethyl)-2-methylbenzimidazolium bromide. 6.5-Chloro-3-(2-formylethyl)-2-methylbenzothiazolium bromide. 7.3-(2-Formylethyl)-5-methoxy-2-methylbenzothiazolium bromide. 8.5,6-Dimethoxy-3-(2-formylethyl)-2-methylbenzothiazolium bromide. 9.3-(2-Formylethyl)-2-methylnaphtho(2,3-d)thiazolium bromide. 10.1-(2-Formylethyl)-4-methylquinolium iodide.